Photographic element



United States Patent() PHOTOGRAPHIC ELEMENT George W. Sawdey and Anthony Loria, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application October 31, 1952, Serial No. 317,904

Claims. (Cl. 95-2) l This invention relates to new products and new photo- `graphic elements protected against the harmful effects of ultraviolet radiation.

`It is known that certain materials such as cellulosic films and photographic layers are adversely affected by ultraviolet radiation when such materials are exposed to daylight. In the case of photographic layers, the ultraviolet radiation sometimes causes undesiredexposure of the layer, or layers, since photographic silver halide emulsions are sensitive to blue, Violet and ultraviolet regions of the spectrum, in addition to any other sensitivity which may be given them, and in the exposure of such material, it is frequently desirable to prevent the action of ultraviolet light on the sensitive emulsion. This is especially true in the case of photographic materials designed for use in color photography where the film has been sensitized to the longer wavelength regions where it is desirable to record only the rays of the visible spectrum.

Color photographs on multilayer photographic material, particularly where the dye images are formed in `sensitive emulsion layers by color development, are susceptible to fading and discoloration by `the action of ultraviolet radiation to which the photographs are subjected during viewing. It is also known that the residual couplers contained in the emulsion layers after formation ofthe picture images in certain processes are attacked by ultraviolet radiation and form a stain which is undesirable in the finished photograph. The action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper or other opaque supports, since this type of print is frequently viewed in daylight where there is a high content of ultraviolet radiation. This dye fading and yellowing appears to be caused primarily by those wavelengths of light which lie close to the visual region of the spectrum, i. e. 360-400 millimicrons.

We have now found that certain new ultraviolet absorbing compounds can be used to overcome the afore-mentioned difficulties, without attendant harmful action by the ultraviolet absorbing compound itself.

It is, therefore, an object of our invention to provide new compounds and photographic elements protected against the harmful effects of ultraviolet radiation. A further object is to provide photographic color materials which have been protected against the harmfuleffects of ultraviolet radiation. Other objects will become apparent from a consideration of the following description.

The new ultraviolet absorbing compounds which we f.

propose to employ in our invention are advantageously represented by the following general formula:

0 @Qa-Q 0 R NHd-Ri wherein R represents an alkyl (e. g. methyl, ethyl, propyl,

isopropyl, n-butyl, n-amyl, n-hexyl, n-dodecyl, etcg) group Y Patented Sept. 27, 1955 rice or an alkoxyl (e. g. methoxyl, ethoxyl, etc.) group, and R1 represents an organic group selectedV from the group consisting of an aryl group and an aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of sulfo (including alkali metal salts thereof, e. g. sodium, potassium, etc.), and carboxyl (including alkali metal salts thereof, e. g. sodium, potassium, etc.), e. g. o, m, and p-sulfophenyl, o, m, and p-carboxyphenyl, 3,5-dicarboxyphenoxymethyl, etc.

The accompanying drawing illustrates schematically a cross-sectional view of a sensitive photographic element having an ultraviolet filter layer containing one of the compounds represented by the above general formula. These ultraviolet absorbingy compounds can be incorporated in the photographic element in a variety of ways, depending on the ultimate use of the photographic element and the degree of protection desired. Advantageously, the ultraviolet absorbing compound can be dissolved or dispersed in a solvent medium together with a colloidal binder, such as gelatin, cellulose esters (e. g. cellulose acetate, etc.), synthetic resins (e. g. polyvinyl acetals, hydrolyzed polyvinyl acetate, etc.), etc., and the resulting mixture coated over the light-sensitive layer of the photographic element. Where the photographic element is a material intended for use in color photography, the ultraviolet filter layer need not be an outer layer, but this layer can be placed over one of the layers subject to the harmful effects of ultraviolet radiation. For example, in a multilayer material comprising three differentially sensitized layers, the red sensitive layer being adjacent to the support, the green sensitive layer being superposed on the red sensitive layer, and the blue sensitive layer being outermost with respect to the other light-sensitive layers, the ultraviolet filter layer can be placed between the blue and green sensitive layers. Alternatively, the ultraviolet filter layer can be placed between the green and the red sensitive layers. If desired, the material useful in absorbing the ultraviolet radiation can be incorporated directly in the light-sensitive emulsion instead of, or in addition to, being present in another layer. 'I'he amount of ultraviolet absorbing compound used can be varied, depending upon the effect desired and the use to which the material is to be put.

The support of the photographic element can be transparent, such as a cellulose ester support, or the support can be opaque, such as a` paper support. Other supports, such as glass, metal, etc., can lbe employed, if desired.

Typical compounds selected from those represented by Formula I which can be used in practicing our invention comprise those represented by the following formulas:

I O H I I C Ha NH-(ll- S 03H 4- 3- 3sulfobenzamido benzoyl] -G-rnethylresorcinol 4) O H O O H 0 -iiii1-0 H 0 I Il C1zH25(11) NH- -CHzO- -O H II O 4-{3- [a- 3,5-dicarboxyphenoxy) acetamido] benzoy1}6n dodecylresorcinol (s) on 0 Ho- -bb-on IO I Hann NH-(i-oHiO- 6 OH (I) fio-@a- I OCZH, NH-

SOaH 4- [3- (3-sulfobenzan1ido benzoyl -6-eth0xyresorcuol The compounds represented by Formula I above can advantageously be prepared by condensing together a compound selected from those represented by the following general formula:

with a compound selected from those of the following general formula:

III o I R I X wherein R and R1 have the values given above and X represents a halogen atom, e. g. chlorine, bromine, etc. The condensations can advantageously be effected in the presence of a diluent, e. g. acetonitrile, 1,4-dioxane, etc. Heating is not generally necessary, since the reaction is exothermic.

The intermediates II can be prepared by reduction of the corresponding nitro derivatives:

IV OH I (I) HO-Q-@ wherein R has the values given above. The reduction can advantageously be effected with hydrogen using Raney nickel catalyst. Intermediates IV can advantageously be obtained by the Hoesch synthesis (by reaction of the resorcinol compound with 1-cyano-3-n'itrobenzene). See Organic Reactions, vol. 5, pp. 387-412.

The sulfo compounds can advantageously be obtained in the form of the sulfonic acid chloride, which undergoes hydrolysis in the presence of the water present in the bathing or coating solutions. In like manner, the 3,5-dicarboxyphenoxymethyl (R1) compounds are iirst obtained in the form of their alkyl esters (e. g. methyl, ethyl, etc.), which can be easily hydrolyzed in aqueous alkali (e. g. sodium hydroxide, sodium carbonate, etc.) to the salts of the respective carboxylic acids.

The following examples will serve to illustrate the manner whereby the new compounds represented by Formula I can be prepared.

Example 1.-4-{3-[a-(3,5-dcarboxyphenoxy)acetamdo]benzoyl}--n-hexylresorcinol (sodium salt) I 0 HO- ii I CoHMu) (IJ-ONa 4-n-hexylresorcinol was prepared according to the method of Desai et al.-Proc. Indian Acad. Sci., vol. 13A, pages 177-83 (Chemical Abstracts, vol. 36, page The 4-n-hexylresorcinol was then condensed by the Hoesch reaction with l-cyano-S-nitrobenzene, according to directions given by Yamashita (Bull. of the Chem. Soc. of Japan, No. 7, vol. 3, page 180). The substituted benzophenone thus produced had the following formula and melted at -96" C.

O @Qa-Q CeHis (Il) NO2 The above compound was then catalytically reduced in the presence of Raney nickel under a hydrogen pressure of 42 pounds to produce the corresponding amino derivative. This amino derivative was crystallized from a mixture of benzene-heptane (2:1) and it had a melting point of 68-70" C.

4.2 g. of the above amine (0.0134 mole) melting at 68-70" C. were dissolved in 25 ml. of acetonitrile and treated with a solution of 3.84 g. (0.0134 mole) of a- (3,5-dicarbomethoxyphenoxy) acetyl chloride in 25 ml. of acetonitrile. There was a rise of 10 (C.) on mixing the solutions and a copius quantity of hydrochloric acid gas was evolved. The resulting solution was then heated at 65 C. for l0 minutes and allowed to stand for one hour. The solution was then filtered and cooled to 5-10 C. The dimethyl ester of the desired product precipitated, and it was filtered and recrystallized from fresh acetonitrile. There were thus obtained 4.8 g. of white plates melting at l46-148 C. On analysis, the following results were obtained:

The dimethyl ester thus obtained was suspended in alcoholic alkali and shaken at room temperature for several minutes. Spontaneous hydrolysis of the dimethyl ester occurred, yielding the sodium salt of the desired acid. This sodium salt can be used directly, or the reaction medium brought to a neutral pH.

The a (3,5 dicarbomethoxyphenoxy)acetal chloride used in the above example was prepared by condensing 5-hydroxyisophthalic acid dimethyl ester with the sodium salt of chloroacetic acid in the presence of sodium methoxide. The sodium salt of the resulting substituted phenoxy acetic acid was treated with phosphorous pentachloride (in ligroin) to yield the desired acid chloride. The 5hy droxyisophthalic acid dimethyl ester was obtained by treating 5-hydroxyisophthalic acid with sulfonylchloride to produce the dicarboxylic acid chloride, followed by treatment with methanol.

This compound was prepared in the same manner as that of Example 1 above, except that -n-dodecylresorcinol was employed in place of the -n-hexylresorcinol of Example 1.

The dimethyl ester of the desired compound had a melting point of 146-148" C.,-and the following results were obtained upon analysis:

Calculated for C31H45N0n Found Percent Percent The dimethyl ester was spontaneously hydrolyzed to the sodium salt of the desired acid by suspending the dimethyl ester in an alcoholic lalkali solution. The sodium salt of the acid was thus obtained.

Calculated for oznzorNods Found Percent Percent C 60. 5 60. 4 5. 1 5. 0 6. 9 7. 0 2. 7 `2. 7 6. 2 6. 3

The chlorosulfonyl compound thus produced was suspended in an alcoholic alkali solution, thus yielding the desired sodium salt.

Example 4.-Applicati0n to photographic element l g. of the chlorosulfonyl compound obtained in Example 3, having a melting point of 15G-151 C., was dissolved in a mixture of 6 ml. of ethyl alcohol and 5 ml. of aqueous vsodium hydroxide, containing 10% by weight of the sodium hydroxide. This solution was added to 89 ml. of water and the pH of the solution adjusted to 7.0 by the addition of citric acid.

Processed film or paper strips were then bathed in the above solution for l0 minutes, and `thereafter rinsed and dried. Measurement of the density of the film or paper strips indicated that an appreciable density to ultraviolet light had been acquired. Exposure of the films or strips to the deleterious effects of daylight caused no detectable deterioration of the photographic images present in the processed `film or paper strips.

In a manner similar to that illustrated in Example 4, photographic elements containing a photographic silver halide emulsion layer can be treated with other ultraviolet absorbing compounds embraced by Formula I above.

The accompanying drawing illustrates schematically a cross-sectional View of a photographic element containing a layer having incorporated therein the sodium salt of 4 [3 (3 sulfobenzamido)benzoyl] 6 n hexylresorcinol, which is representative of the ultraviolet absorbing agents which can be employed in our invention. As shown in the single ligure of the drawing, a support 10 of any suitable material, such as cellulose acetate, or paper, having thereon an emulsionlayer 11 is coated with a iilter layer 12 having incorporated therein the sodium salt of 4 [3 (3 sulfobenzamido)benzoyl] 6 n hexylrescorcinol, or some other ultraviolet absorbing compound selected from those represented by the above general Formula I. It will be understood that the drawing is merely representative of other structures which can be employed in our invention, and that the element can have other layers, not shown, such as additional light-sensitive layers, subbing layers, antihalation layers, etc.

As noted above, it has been found to be especially advantageous to incorporate the water-soluble ultraviolet absorbing compounds of our invention into the photographic element by simply bathing the element in an'aqueous solution containing the ultraviolet absorbing cornpound. Where the outer layer contains gelatin, the ultraviolet absorbing compound becomes adsorbed to this layer. By incorporating a resinous mordant, e. g. polyvinyl pyridine methyl p-toluenesulfonate, phenol-formaldehyde ion exchange resins, etc. in the outer gelatin layer (or an intermediate layer where desired), the photographic element can be subjected to washing or processing operations without removal of the ultraviolet absorbing compounds. Thus, the ultraviolet absorbing compounds can be incorporated into the photographic element before or after (i. e. during processing) exposure.

if desired, the material used in absorbing the ultraviolet radiation can be incorporated directly in the light-sensitive emulsion instead of, or in addition to, being present in a separate filter layer. Generally, it is more advantageous to incorporate such ultraviolet absorbing compounds in a separate lter layer, however.

What we claim as our invention and desire secured by Letters Patent of the United States is:

1. A photographic element comprising a support, at least one photographic silver halide emulsion layer, and incorporated in one of the layers of said photographic element a compound selected from those represented by the following general formula:

wherein R represents a member selected from the group consisting of an alkyl group and an alkoxyl group, and R1 represents an organic group selected from the group consisting of an aryl group and an aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of a sulfo group, a carboxyl group and an alkali metal salt of said radicals.

2. A photographic element comprising a support, at least one photographic gelatino-silver halide emulsion layer, and incorporated in one of the layers of said photographic element a compound selected from those represented by the following general formula:

wherein R represents a member selected from the group consisting of an alkyl group containing from 1 to 12 carbon atoms and an alkoxyl group containing from 1 to 2 carbon atoms, and R1 represents an organic group selected from the group consisting of a monocyclic aryl group and a monocyclic aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of a sulfo group, a carboxyl group and an alkali metal salt of said radicals.

3. A photographic element comprising a support, at least one photographic gelatino-silver halide emulsion layer, and coated over said photographic gelatino-silver halide emulsion layer, a gelatin layer containing a compound selected from those represented by the following general formula:

wherein R represents a member selected from the group consisting of an alkyl group containing from 1 to 12 carbon atoms and an alkoxyl group containing from 1 to 2 carbon atoms, and R1 represents an organic group selected from the group consisting of a monocyclic aryl group and a monocyclic aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of a sulfo group, a carboxyl group and an alkali metal salt of said radicals.

4. A linished photographic element comprising a support having thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, atleast one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layei containing an ultraviolet absorbing compound selected from those represented by the following general formula:

| o Hoil i R NH-Ri wherein- R represents a member selected from the group consisting of an alkyl group containing from 1 to 12 carbon atoms and an alkoxyl group containing from l to 2 carbon atoms, and R1 represents an organic group selected said photographic gelatine-silver halide emulsion layer lying between said support and said gelatin layer.

7. A photographic element comprising a support, a photographic gelatino-silver halide emulsion layer, and a gelatin layer containing the sodium salt of a compound having the following formula:

il LOB having the following formula:

O ma@ said photographic gelatino-silver halide emulsion layer lying between said supoprt and said gelatin layer.

9. A method of preventing image degradation in a nished photographic element comprising a plurality of developed and xed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin outer layer, which comprises applying to said photographic element from aqueous, non-colloidal solution an ultraviolet radiation absorbing compound selected from those represented by the following general formula:

0 R NH-Ri wherein R represents a member selected from the group consisting of an alkyl group and an alkoxyl group, and R1 represents an organic group selected from the group consisting of an aryl group and an aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of a sulfo group, a carboxyl group and an alkali metal salt of said radicals.

l0. A process of incorporating an ultraviolet absorbing compound into a photographic element comprising bathing said photographic element in an aqueous, non-colloidal solution of a compound selected from those represented by the following general formula:

n lit NHG-R1 wherein R represents a member selected from the group consisting of an alkyl group and an alkoxyl group, and R1 represents an organic group selected from the group consisting of an aryl group and an aryloxymethyl group, said organic group being substituted by a radical selected from the group consisting of a sulfo group, a carboxyl group and an alkali metal salt of said radicals, said photographic element comprising a support, at least one photographic silver halide emulsion layer, and an outer gelatin layer.

References Cited in the le of this patent UNITED STATES PATENTS 1,915,429 Laska et al. June 27, 1933 2,160,907 Richardson June 6, 1939 2,241,239 Carroll et al. May 6, 1941 2,389,147 Friedheim Nov. 20, 1945 

1. A PHOTOGRAPHIC ELEMENT ELEMENT COMPRISING A SUPPORT, AT LEAST ONE PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER, AND INCORPORATED IN ONE OF THE LAYERS OF SAID PHOTOGRAPHIC ELEMENT A COMPOUND SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 